Nondiffusing acylacetyl sulphonamide coupler



Patented May 30, 1944 UNITED STATES PATENT, orF-iea NONDIFFUSING ACYLACETYL-SULPHON- AMIDE COUPLER.

Arnold Weissberger, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Original application August 22,

1940, Serial No. 353,669. plication August 6, 1942, Serial No. 453,854. In

Great Britain April 24, 1940 Claims.

This invention relates to photographic color forming compounds and particularly to nondifiusing acylacetyl coupler compounds containing sulphonainide groups for incorporation in photographic emulsion layers.

This application is a division of my application Serial No. 353,669, filed August 22, 1940, now

' Patent 2,298,443, granted October 13, 1942.

Color forming compounds which react with the development product of aromatic amino developing agents to form colored images on photo-, graphic development have been the subject of numerous prior patents. The dyes formed in this way are insoluble in water and in the ordinary' photographic developing and fixing baths al-. though the silver images formed simultaneously with them during the photographic development may be removed from the photographic layer to leave pure dye images in the layer. Such a. compound which is employed in conjunction with the developing agent for the silver and which couples with the development product of the developer during photographic development is referred to herein as a coupling component or coupler. When these coupling components are incorporated in the photographic layer prior to exposure; they do not afiect the exposure and development of the layer in the usual way but when the development is carried out with a suitable developing agent they combine with the oxidation product of the developer to form a colored image in situ with the silver image.

In Vittum, Peterson and Porter U. S. Patent No. 2,271,238, granted January 27, 1942, coupling components are described which contain sulphonamide groups. Such couplers are desirable by reason of their solubility characteristics and the improved properties of the dyes formed from them. The couplers described in the Vittum, Peterson and Porter patent are, in general, soluble in the developing solution and not suitable for use in the emulsion layer because of their tendency to diflfuse from the layer. The dyes formed from these couplers, however, have better light transmission characteristics and are more stable to heat and light than the dyes produced from previously known coupling components.

It is an object or the present invention to provide coupling components which have the desirable properties of couplers containing the sulphonamide group but which may be incoiporated in photographic emulsion layers as non-diii'using compounds. A further object is to provide novel photographic couplers having desirable properties with respect to heat and light stability. A

Divided and this apa I B'COCH:C ONHOSOz-N -R in which R=aryl R'-=alkyl, aryi Y=allql, aryl.

My invention may be illustrated by reference to the following Compounds I and II.

NKC O-UHr-C 0-0015 Il a BOr-N-CaH s Compound I is acoupler capable of producing a yellow dye image and is of the type-described in Vitturn, Peterson and Porter U. S. Patent No. 2,271,238. It is soluble in photographic developing solutions; Compound 11 is identical with Compound I except that the free hydrogen atom of the sulphonamide group has been replaced with a methyl radical. Compound 11 also products a yellow dye upon development with the proper N-methyi-p-(benzoylaoetamino)-benzencsulphon-p-nltroanilide photographic developing agent. However, because of the replacement of the hydrogen atom of the sulphonated group with a suitable radical, the coupler is no longer soluble in the developer but may be incorporated in a photographic emulsion layer as a non-diilfusing compound. My invention resides in the discovery that, by the substitution of this free hydrogen atom of the sulphonamidegroup with suitable organic' radicals, the valuable properties of the sulphonamide couplers may be retained, but the solubility properties of the coupler are materially altered and the coupler is rendered non-diffusing in gelatin or other colloidal media.

Compounds suitable for use as non-diil'using couplers according to my invention are as follows:

NH-C mom-c G N-(p-benzoylacetaminobenzenesnlphonyl)-N-methylaniline 13mm ONBOr-NH-O o-cm-c 0Q N-(p-benzoylaoetamlnobenzenesulphonyl)-N-iso amylnniline N-(p-benzo laoetaminobenzenomlphon l)-N-eth l naphthylamina y y w nncodmco-O Cali:

(a) Q-COOHzCOHNON-QWQ-CH;

HI p-benzoylaoetamino N-(ntoluenesulpbonyl)-N-mothylanilina (6) Q-ooomc oNnOsot-I-Oommm.)

nsBn N-(p benzoylacatamlnobenzenosmlillglionyl)-N-(n-amyl)-p-tert.-

amyl a .(1) Q-CDCHaCONH-O-Qdg-N-O v v I 7 an" I N -(p benzoy1acetaminobenzenesnlphonyl)-N-iomylanilin a (a) OcocniooNn-o-soriicmrc N-(p-benzoylacetaminobenzoneanlphonyl) N-(-rphenylpropyhaniline N-(p-benfoylaoataminobenzanesnlphonyll-N-benzybphluldihe 45 cnUiI-m8-O-Nnc0cmc 0-0-0011.

, -Omoomcorr Osorn-(oHm-O terL-OHu N-(p-benzoylaoetaminobenzenesulphonyl)-N-(- -phenyl top I)- p-terL-amylimllilw. p y n) m O0ocniconn-o-sorirocmuaee.)

I1- Hi1 is o OOCmGONHOQQ-N-CHFQ r 270B! N-(p-bonzoylaoetaminobephonyD-N-benzyianilina (1a) Ococmc ONHOBbr-NOCsHMtert.)

- aCfln N-(p-benzoylaataminobenzenmflglionyD-N(benzyl)-p-tert.- 2.5 a

Lxr

7 CH: N-( benzoylamtsminobenunesul honyl -N-( henyl :0 yl)- 0);tollflne W p p 1:- 5H" all) I N-( bcnzo lacetsminobenzenesul l-N-n-om ipy o)-toluidins phony) y N -(banisoylooetominobenzenostflionylkN-benzyl-m-toluidina N-(p-benzoylaoetaminobenzenesulphonyl)-N-benzyl-m-toluidine gafjcm-N-oaOnncocmoo-Oocm oHa N-(' loom benmmml h of v gn-methylbznsylmilige (19) o Qcmdmcirn-oaO-mzcocmco I N- ylacetaminobenzenesul ho -N- heal 1- (P911180 g (w-n yompy) themselves.

In these compounds the CH: group attached,

to the two carbonyl groups is reactive with primary aromatic amino developing agents in the development process. One of the hydrogen atoms of the methylene group may, in general, be substituted by certain groups without destroying the chemical activity of the group.

The aromatic amino developing agents used with the coupler compounds of my invention include the mono-, di and triaminoaryl compounds and their derivatives formed by substitution in the amino group as well as inthe ring, such as alkylphenylenediamines and alkyltoluylenediamines. These compounds are usually used in the salt form, such as the hydrochloride or the 1- sulphate, which are more stable than the amines Suitable compounds are diethyl-pphenylenediamine hydrochloride, monomethylp-phenylenediaminehydrochloride, dimethyl-pphenylenediaminehydrochloride and dimethyl-pphenylenediamine sulphate. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted.

Example 1, p-Aminodiethylaniline sulphate grams 2.5 Sodium sulphite anhydrous --do 2 Sodium carbonate anhydrous do 20 Potassium bromide do' 1 water in liter 1 Example 2 p-Aminodiethylaniline hydrochloride grams 2 Sodium sulphite anhydrous do e 5 Sodium carbonate anhydrous do Potassium br e do 2 Water to liter 1 The couplers used according to my invention may be incorporated in silver halide emulsion layers in various ways but I prefer to form a solution of the sodium salt of the coupler in alcohol and add this to the emulsion. For example, 3 grams of coupler may be dissolved or suspended in 50 cc. of ethyl alcohol and sodium hydroxide added in the amount of 1 equivalent weights of the coupler. The sodium hydroxide may be added as solid or as a concentrate solution. The sodium salt of the coupler is thereby generated in a solution of 50 cc. of alcohol and this solution is added to 1 liter of a gelatin silver haiide emulsion. The pH of the emulsion may then' be adjusted if desired by adding a suitable acid such as acetic or sulphuric acid to neutralize all or part of the sodium hydroxide used to form the sodium salt of the coupler.

The coupling components may be incorporated either in gelatin or in other colloidal materials such as collodion, organic esters of cellulose or synthetic resins. The emulsion may be carried by a transparent medium such as glass, cellulose ester, or synthetic resin or a non-transparent refleeting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single layer on the support or superposed layers containing the couplers may be coated on one or both sides of the support. The superwhere R is an aryl radical, R is selected from the posed layers may be difierentially sensitized tor the formation of a natural color image in the well known manner.

The exam les and compounds set forth in the present specification are illustrative only and it is to be understood that my invention is to be taken as limited only by the scope of the appended claims.

I claim:

1. A photographic emulsion for forming colored images comprising. a colloidal carrier con-- taining a sensitive silver halide and a coupler compound having a formula selected from the class consisting of I iv-c o cine oNnON-s oi-a and class consisting of alkyl and aryl radicals and Y is selected from the class consisting of alkyl and aryl radicals.

2. A photographic emulsion for forming colored images comprising a colloidal carrier containing a sensitive silver .halide and a coupler having a formula selected from the class consisting of Y ooomoomrO I -s Oz-R and r i Q Y O0 0 arm: ONH -s'o,1-I-R where R is an aryl radical and Y i selected from the class consisting of alkyl and aryl radicals.

3. A photographic emulsion for forming coloredimages comprising a colloidal carrier containing a sensitive silver halide and a coupler having a formula selected from the class consisting of Y 000 omo ONH-Ol IS Or-R Y 7 I Q0 0 cine ONHOl ISOi-R where R is an aryl radical and Y is an aryl substituted alkyl radical. v

the Iormul 6.A photographic emulsion for forming colored images comprising a gelatino silver halide emulsion containing a coupler compound having where R is an aryl radical and Y is an aryl substituted alkyl radical.

7. A photographic emulsion for forming coiored images comprising a gelatino-silver'halide emulsion containing a coupler compound having the formula:

. I v @rv-so-Qnn-co-cm-coQ 8. A photographic emulsion for forming colored images comprising a gelatlno-silver-halide emulsion containing a coupler compound having the formula:

I 9. In the method of producing a colored photographic image in a gelatino-silver halide emulsion layer the step which comprises treating the exposed layer containing -a coupler compound having a-iormula selected from the class consisting of I I R'cocmc oNnON-s Or-R I Y '-oocnlo ONE-Q S O:i l'R where R is an aryl radical; R is selected from the class consisting of alkyl and aryl radicals and Y is selected from the class consisting of alkyl and and aryl radicals, with a developer containing a primary aromatic amino developing agent.

10. In the method of producing a colored photographic image in a gelatino-silver halide emulsion layer the step which comprises treating the exposed layer containing a coupler compound having a formula selected from the class consisting oi where R is an'aryl the class consisting of alkyl and aryl radicals with a developer containing a primary aromatic v amino developing agent.

' ARNOLD WEISSBERGER.

l radical and Y is selected fromv 

